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United States Patent |
5,698,024
|
Badejo
,   et al.
|
December 16, 1997
|
Organic pigment compositions
Abstract
This invention relates to pigment compositions comprising an organic
pigment treated with about 0.1 to about 20% by weight, based on the
organic pigment, of a compound having the formula (I)
##STR1##
wherein Q represents an organic pigment moiety,
X is O or S,
Het represents a heteroaromatic group attached at a ring carbon atom to the
(thio)amidomethyl --CH.sub.2 --NH--CX-- linking group, and
n is from 1 to 4.
Inventors:
|
Badejo; Ibraheem T. (N. Charleston, SC);
Rice; Daphne J. (Charleston, SC)
|
Assignee:
|
Bayer Corporation (Pittsburgh, PA)
|
Appl. No.:
|
777102 |
Filed:
|
December 31, 1996 |
Current U.S. Class: |
106/495; 106/497; 106/498 |
Intern'l Class: |
C09B 048/00 |
Field of Search: |
106/495,497,498
|
References Cited
U.S. Patent Documents
3418322 | Dec., 1968 | Tulagin et al. | 260/279.
|
3446641 | May., 1969 | Mitchell et al. | 106/288.
|
3635981 | Jan., 1972 | Weinberger | 260/279.
|
4088507 | May., 1978 | Tanaka et al. | 106/288.
|
4197404 | Apr., 1980 | Johnson | 546/49.
|
4256507 | Mar., 1981 | Kranz et al. | 106/288.
|
4310359 | Jan., 1982 | Ehashi et al. | 106/288.
|
4439240 | Mar., 1984 | Ganci | 106/288.
|
4455173 | Jun., 1984 | Jaffe | 106/288.
|
4478968 | Oct., 1984 | Jaffe | 524/88.
|
4541872 | Sep., 1985 | Jaffe | 106/309.
|
4844742 | Jul., 1989 | Jaffe | 106/448.
|
4895948 | Jan., 1990 | Jaffe et al. | 546/56.
|
4895949 | Jan., 1990 | Jaffe et al. | 546/56.
|
5137576 | Aug., 1992 | Macholdt et al. | 106/495.
|
5194088 | Mar., 1993 | Babler et al. | 106/412.
|
5264032 | Nov., 1993 | Dietz et al. | 106/411.
|
5286863 | Feb., 1994 | Babler et al. | 546/56.
|
5334727 | Aug., 1994 | Campbell | 548/373.
|
5368641 | Nov., 1994 | Dietz et al. | 106/495.
|
5424429 | Jun., 1995 | Hendi et al. | 546/49.
|
5453151 | Sep., 1995 | Babler et al. | 106/497.
|
5457203 | Oct., 1995 | Hendi et al. | 546/56.
|
Foreign Patent Documents |
1544839 | Apr., 1976 | GB.
| |
2009205 | Jun., 1979 | GB.
| |
Primary Examiner: Jones; Deborah
Assistant Examiner: Harding; Amy M.
Attorney, Agent or Firm: Gil; Joseph C., Henderson; Richard E. L.
Claims
What is claimed is:
1. A pigment composition comprising an organic pigment treated with about
0.1 to about 20% by weight, based on the organic pigment, of a pigment
derivative having the formula
##STR12##
wherein Q represents an organic pigment moiety,
X is O or S,
Het represents a heteroaromatic group attached at a ring carbon atom to the
(thio)amidomethyl--CH.sub.2 --NH--CX-- linking group, and
n is from 1 to 4.
2. A pigment composition according to claim 1 wherein the organic pigment
is treated with 1 to 10% by weight of the pigment derivative.
3. A pigment composition according to claim 1 wherein Het is a pyrrole,
imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine,
furan, thiophene, isoxazole, isothiazole, or furazan or derivative thereof
in which one or more ring atoms are substituted with C.sub.1 -C.sub.6
alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.5 -C.sub.7 cycloalkyl, C.sub.5
-C.sub.7 cycloalkoxy, C.sub.6 -C.sub.10 aryl, C.sub.6 -C.sub.10 aryloxy,
C.sub.7 -C.sub.16 aralkyl, C.sub.7 -C.sub.16 aralkoxy, hydroxy, halogen,
nitrile, carboxyl or an amide thereof, sulfonyl, or combinations thereof.
4. A pigment composition according to claim 1 wherein the pigment
derivative is
(a) a nicotinamidomethylquinacridone or thionicotinamidomethylquinacridone
having the formula
##STR13##
wherein X is O or S and n is 1 or 2; (b) a 2-furamidomethyl-substituted
quinacridone having the formula
##STR14##
or (c) a 2-thiophenecarboxamidomethylquinacridone having the formula
##STR15##
5. A pigment composition according to claim 4 wherein the organic pigment
is a quinacridone.
6. A pigment composition according to claim 1 wherein the organic pigment
is treated by
(a) mixing a crude organic pigment with a heteroarylamidomethyl and/or
heteroarylthioamidomethyl pigment derivative in a strong mineral acid,
(b) wet or dry blending a crude or finished organic pigment with a
heteroarylamidomethyl and/or heteroarylthioamidomethyl pigment derivative,
(c) adding a heteroarylamidomethyl and/or heteroarylthioamidomethyl pigment
derivative during synthesis of the organic pigment,
(d) conditioning an organic pigment in the presence of a
heteroarylamidomethyl and/or heteroarylthioamidomethyl pigment derivative,
or
(e) a combination of one or more of methods (a), (b), (c), and (d).
7. A pigmented paint containing a pigment composition according to claim 1.
8. A pigmented plastic containing a pigment composition according to claim
1.
9. An ink containing as pigment a pigment composition according to claim 1.
10. A toner containing as pigment a pigment composition according to claim
1.
Description
BACKGROUND OF THE INVENTION
This invention relates to pigment compositions obtained by treating organic
pigments with heteroarylamidomethyl and/or heteroarylthioamidomethyl
pigment derivatives that impart improved rheological properties and
dispersibility.
Many types of organic pigments are known and each can be prepared by one or
more known methods. Typically, however, the initially formed crude
compounds are unsuitable for use as pigments and must undergo one or more
additional finishing steps to modify the particle size, particle shape, or
crystal structure to achieve suitable pigmentary quality, rheological
properties, and dispersibility.
Methods to improve rheological properties are known. For example, pigments
can be treated with various additives, such as sulfonic acid and
sulfonamide derivatives of various pigments. E.g., U.S. Pat. Nos.
3,418,322, 3,446,641, 4,088,507, 4,310,359, and 5,368,641 and British
Patents 1,544,839 and 2,009,205.
Other pigment derivatives have also been disclosed for use as pigment
additives. For example, pyrazolylmethyl quinacridone derivatives are
described in U.S. Pat. No. 5,334,727. This patent, however, does not
suggest the introduction of an amido or thioamido functionality between
the heterocyclic ring and the methyl group, a critical feature of the
present invention. Substituted benzamidomethyl quinacridones and
structurally related phthalimidomethyl and sulfobenzimidomethyl
quinacridones are described in U.S. Pat. Nos. 3,635,981, 4,197,404,
4,256,507, 4,439,240, 4,455,173, 4,478,968, 4,541,872, 4,844,742,
4,895,949, 5,194,088, 5,264,032, 5,286,863, 5,424,429, 5,453,151, and
5,457,203. These patents, however, disclose compounds in which amide
carbonyl groups are attached only to benzene rings and do not suggest
attachment to heterocycles, another critical feature of the present
invention.
It has now surprisingly been found that pigment compositions having
excellent pigmentary quality and rheological properties can be obtained by
treating organic pigments with certain pigment derivatives bearing one or
more heteroarylamidomethyl and/or heteroarylthioamidomethyl substituents
in which the carbonyl function of each (thio)amidomethyl linking group is
attached at a ring carbon atom of the heteroaromatic group. Such
advantages are found even in comparison to benzamidomethyl quinacridones.
SUMMARY OF THE INVENTION
This invention relates to pigment compositions comprising an organic
pigment treated with about 0.1 to about 20% by weight (preferably 1 to 10%
by weight), based on the organic pigment, of a pigment derivative having
the formula (I)
##STR2##
wherein Q represents an organic pigment moiety,
X is O or S,
Het represents a heteroaromatic group attached at a ring carbon atom to the
(thio)amidomethyl --CH.sub.2 --NH--CX-- linking group, and
n is from 1 to 4.
This invention further relates to processes for preparing such pigment
compositions and to the use of such pigment compositions in the
pigmentation of paints, plastics, fibers, inks, and toners.
DETAILED DESCRIPTION OF THE INVENTION
Suitable organic pigments that can be treated by the process of the present
invention include quinacridone, phthalocyanine, and perylene pigments, as
well as other known organic pigments. Mixtures, including solid solutions,
of such pigments are also suitable.
Quinacridone pigments are particularly suitable organic pigments.
Quinacridones (which, as used herein, includes unsubstituted quinacridone,
quinacridone derivatives, and solid solutions thereof) can be prepared by
any of several methods known in the art but are preferably prepared by
thermally ring-closing various 2,5-dianilinoterephthalic acid precursors
in the presence of polyphosphoric acid. E.g., S. S. Labana and L. L.
Labana, "Quinacridones" in Chemical Review, 67, 1-18 (1967), and U.S. Pat.
Nos. 3,157,659, 3,256,285, 3,257,405, and 3,317,539. Suitable quinacridone
pigments can be unsubstituted or substituted (for example, with one or
more alkyl, alkoxy, halogens such as chlorine, or other substituents
typical of quinacridone pigments).
Metal phthalocyanine pigments are also suitable organic pigments. Although
copper phthalocyanines are preferred, other metal-containing
phthalocyanine pigments, such as those based on zinc, cobalt, iron,
nickel, and other such metals, may also be used. Suitable phthalocyanine
pigments can be unsubstituted or partially substituted (for example, with
one or more alkyl, alkoxy, halogens such as chlorine, or other
substituents typical of phthalocyanine pigments). Crude phthalocyanines
can be prepared by any of several methods known in the art but are
preferably prepared by a reaction of phthalic anhydride, phthalonitrile or
derivatives thereof with a metal donor, a nitrogen donor (such as urea or
the phthalonitrile itself), and an optional catalyst, preferably in an
organic solvent. E.g., W. Herbst and K. Hunger, Industrial Organic
Pigments (New York: VCH Publishers, Inc., 1993), pages 418-427, H.
Zollinger, Color Chemistry (VCH Verlagsgessellschaft, 1973), pages
101-104, and N. M. Bigelow and M. A. Perkins, "Phthalocyanine Pigments" in
The Chemistry of Synthetic Dyes and Pigments, ed. H. A. Lubs (Malabar,
Fla.: Robert E. Krieger Publishing Company, 1955), pages 584-587; see also
U.S. Pat. Nos. 4,158,572, 4,257,951, and 5,175,282 and British Patent
1,502,884.
Perylenes, particularly the diimides and dianhydrides of
perylene-3,4,9,10-tetracarboxylic acid, are also suitable organic
pigments. Suitable perylene pigments can be unsubstituted or substituted
(for example, with one or more alkyl, alkoxy, halogens such as chlorine,
or other substituents typical of perylene pigments), including those
substituted at imide nitrogen atoms with chemically reasonable groups such
as alkyl. Crude perylenes can be prepared by methods known in the art.
E.g., W. Herbst and K. Hunger, Industrial Organic Pigments (New York: VCH
Publishers, Inc., 1993), pages 9 and 467-475, H. Zollinger, Color
Chemistry (VCH Verlagsgessellschaft, 1973), pages 227-228 and 297-298, and
M. A. Perkins, "Pyridines and Pyridones" in The Chemistry of Synthetic
Dyes and Pigments, ed. H. A. Lubs (Malabar, Fla.: Robert E. Krieger
Publishing Company, 1955), pages 481-482.
Other suitable organic pigments include dioxazines (that is,
triphenedioxazines), 1,4-diketopyrrolopyrroles, anthrapyrimidines,
anthanthrones, flavanthrones, indanthrones, isoindolines, isoindolinones,
perinones, pyranthrones, thioindigos, 4,4'-diamino-1,1'-dianthraquinonyl,
and azo compounds, as well as substituted derivatives.
The organic pigments can be treated according to the invention, for
example, by mixing crude organic pigments with heteroarylamidomethyl
and/or heteroarylthioamidomethyl pigment derivatives in a strong mineral
acid, by wet or dry blending crude or finished organic pigments with the
pigment derivatives, or by adding the pigment derivatives during pigment
synthesis. It is also possible to treat organic pigments by conditioning
in the presence of heteroarylamidomethyl and heteroarylthioamidomethyl
pigment derivatives. Combinations of such methods are also suitable.
Suitable heteroarylamidomethyl and heteroarylthioamidomethyl pigment
derivatives are compounds having the formula (I)
##STR3##
in which Q is represents an organic pigment moiety; X represents O (for
amidomethyl linking groups) or S (for thioamidomethyl linking groups); Het
represents a heteroaromatic group attached at a ring carbon atom to the
carbonyl or thiocarbonyl function of the (thio)amidomethyl (i.e.,
--CH.sub.2 --NH--CX--) linking group; and n is from 1 to 4 (preferably 1
or 2, more preferably 1).
Pigment moiety Q can be derived from essentially any class of organic
pigments, including quinacridones, phthalocyanines, perylenes
(particularly the imides, diimides, anhydrides, and/or dianhydrides of
perylene-3,4,9,10-tetracarboxylic acid), dioxazines (that is,
triphenedioxazines), 1,4-diketopyrrolopyrroles, anthrapyrimidines,
anthanthrones, flavanthrones, indanthrones, isoindolines, isoindolinones,
perinones, pyranthrones, thioindigos, 4,4'-diamino-1,1'-dianthraquinonyl,
or azo compounds, as well as substituted derivatives thereof. Suitable
derivatives include those having one or more substituents that are typical
of such pigments, such as C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy,
C.sub.5 -C.sub.7 cycloalkyl, C.sub.5 -C.sub.7 cycloalkoxy, C.sub.6
-C.sub.10 aryl, C.sub.6 -C.sub.10 aryloxy, C.sub.7 -C.sub.16 aralkyl,
C.sub.7 -C.sub.16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or amides
thereof, sulfonyl (such as alkyl- and arylsulfonyl or sulfoxyl and amides
thereof) groups or combinations thereof. Substituted derivatives of
pigment moiety Q can, of course, include those in which ring nitrogen
atoms are substituted with chemically reasonable groups such as alkyl,
cycloalkyl, aryl, or aralkyl. It is often desirable to use
heteroarylamidomethyl and heteroarylthioamidomethyl pigment derivatives in
which the pigment moiety Q is the same pigment type as the organic pigment
being treated. However, it can often be desirable to use
heteroarylamidomethyl and heteroarylthioamidomethyl pigment derivatives in
which pigment moiety Q is a different pigment type from the organic
pigment being treated. Preferred pigment derivatives are those derived
from quinacridones, phthalocyanines, and perylenes.
Suitable heteroaromatic Het groups are aromatic species that contain one or
more ring heteroatoms (selected from N, O and S) and that are attached at
a ring carbon atom to the (thio)amidomethyl (i.e., --CH.sub.2 --NH--CX--)
linking group. Examples of suitable heteroaromatic Het groups include
those derived from pyrrole, imidazole, pyrazole, pyridine, pyrazine,
pyrimidine, pyridazine, triazine, furan, thiophene, isoxazole,
isothiazole, and furazan or derivatives thereof in which one or more ring
atoms are substituted with C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6
alkoxy, C.sub.5 -C.sub.7 cycloalkyl, C.sub.5 -C.sub.7 cycloalkoxy, C.sub.6
-C.sub.10 aryl, C.sub.6 -C.sub.10 aryloxy, C.sub.7 -C.sub.16 aralkyl,
C.sub.7 -C.sub.16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or amides
thereof, sulfonyl (such as alkyl- and arylsulfonyl or sulfoxyl and amides
thereof) groups or combinations thereof. Although some of the above Het
groups, such as furan, may exhibit a low degree of aromaticity, such
compounds are to be considered heteroaromatic for the purposes of this
invention if no more than one hydrogen atom or substituent is attached to
each ring atom.
As used herein, the term "C.sub.1 -C.sub.6 alkyl" refers to straight or
branched chain aliphatic hydrocarbon groups having from 1 to 6 carbon
atoms. Examples of C.sub.1 -C.sub.6 alkyl are methyl, ethyl, propyl,
butyl, pentyl, hexyl, and the isomeric forms thereof. The term "C.sub.1
-C.sub.6 alkoxy" refers to straight or branched chain alkyl oxy groups
having from 1 to 6 carbon atoms. Examples of C.sub.1 -C.sub.6 alkoxy are
methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the isomeric
forms thereof. The term "C.sub.5 -C.sub.7 cycloalkyl" refers to
cycloaliphatic hydrocarbons groups having from 5 to 7 carbon atoms.
Examples of C.sub.5 -C.sub.7 cycloalkyl are cyclopentyl, cyclohexyl, and
cycloheptyl. The term "C.sub.5 -C.sub.7 cycloalkoxy" refers to
cycloalkyloxy groups having from 5 to 7 carbon atoms. Examples of C.sub.5
-C.sub.7 cycloalkoxy are cyclopentyloxy, cyclohexyloxy, and
cycloheptyloxy. The term "C.sub.6 -C10 aryl" refers to phenyl and 1- or
2-naphthyl, as well as to phenyl and naphthyl groups substituted with
alkyl, alkoxy, halogen, cyano, as defined herein. The term "C.sub.6 -C10
aryloxy" refers to phenoxy and 1- or 2-naphthoxy, in which the aryl
portion can optionally be substituted as described above for "aryl." The
term "C.sub.7 -C16 aralkyl" refers to C.sub.1 -C.sub.6 alkyl substituted
with C.sub.6 -C.sub.10 aryl such that the total number of carbon atoms is
from 7 to 16. Examples of C.sub.7 -C.sub.16 aralkyl are benzyl, phenethyl,
and naphthylmethyl. The term "C.sub.7 -C.sub.16 aralkoxy" refers to
C.sub.1 -C.sub.6 alkoxy substituted with C.sub.6 -C10 aryl such that the
total number of carbon atoms is from 7 to 16. An example of C.sub.7
-C.sub.16 aralkoxy is benzyloxy. Examples of halogen are fluorine,
chlorine, bromine, and iodine. Particularly preferred heteroaromatic Het
groups are those derived from pyridine, furan, and thiophene.
Suitable, but generally less preferred, heteroaromatic Het groups include
polyaromatic derivatives in which one or two pairs of adjacent ring atoms
are fused with one or two aromatic rings (such as benzene or
heteroaromatic analogs thereof) that can themselves be ring-substituted as
described above or contain one or more ring heteroatoms selected from O,
S, and N. Examples of suitable such polyaromatic Het groups include those
based on indole, isoindole, and indolazine (i.e., benzo derivatives of
pyrrole), carbazole (i.e., a dibenzo derivative of pyrrole), indazole,
benzimidazole, quinoline, isoquinoline, and quinolazine (i.e., benzo
derivatives of pyridine), quinazoline, quinoxaline, cinnoline, purine,
benzofuran and isobenzofuran (i.e., benzo derivatives of furan),
phenoxazine, benzothiazine, naphthothiophene, and thianthrene, as well as
ring-substituted derivatives thereof.
The --CH.sub.2 --NH--CX-- linking group can be either an amidomethyl (i.e.,
--CH.sub.2 --NH--CO--) group or a thioamidomethyl (i.e., --CH.sub.2
--NH--CS--) group.
Heteroarylamidomethyl and heteroarylthioamidomethyl pigment derivatives
used according to the invention can be prepared by known methods, for
example, by condensing the pigment to be derivatized with a mixture of a
heteroarylcarboxamide or heteroarylthiocarboxamide or derivative thereof
and formaldehyde or a functional equivalent (such as the polymeric form
paraformaldehyde or a formaldehyde-producing compound such as trioxane) or
with a corresponding N-methylol derivative of a heteroarylcarboxamide or
heteroarylthiocarboxamide in the presence of a dehydrating agent at a
temperature of about 0.degree. to about 200.degree. C. Suitable
dehydrating agents include sulfuric acid, oleum, poly-phosphoric acid,
organic acids or their anhydrides, and mixtures thereof. Oleum is a
particularly suitable condensing agent, especially for the less reactive
pigments. The degree of substitution on the pigment molecule can be
affected by various factors, such as the quantity of
heteroaryl(thio)carboxamide, the reaction temperature, and length of
reaction. The resultant heteroarylamidomethyl or heteroarylthioamidomethyl
pigment derivatives can be isolated by adding the reaction mixture to a
liquid in which the pigment derivative is completely or almost completely
insoluble, preferably water or methanol or other lower aliphatic alcohols
(such as ethanol, propanol, or butanol), as well as mixtures thereof. It
can also be advantageous to include various additives, such as
surfactants, in the liquid. The pigment derivatives are then isolated (for
example, by filtration or other known methods) and washed until free of
residual acid.
Particularly preferred pigment derivatives for treating pigments according
to the invention are nicotinamidomethyl- and
thionicotinamidomethylquinacridones having the formula (II)
##STR4##
wherein X is O or S and n is 1 or 2; 2-furamidomethyl-substituted
quinacridones having the formula (III)
##STR5##
and 2-thiophenecarboxamidomethylquinacridones having the formula (IV)
##STR6##
Formulas (II), (III), and (IV) are not intended to indicate specific
locations for the heteroaryl(thio)amidomethyl groups but rather to
indicate that such groups are located in chemically reasonable positions
of the quinacridone moiety.
Several methods for preparing the pigment compositions of the invention are
known. In one preferred method, a crude organic pigment and a suitable
heteroarylamidomethyl and/or heteroarylthioamidomethyl pigment derivative
are dissolved ("pasted") or suspended ("swelled") in a strong mineral acid
and then precipitated. A sufficient amount of mineral acid, preferably
concentrated acid, is added to insure formation of an acidic solution or
suspension within a reasonable amount of time. However, except for the
requirement that the solution or suspension be acidic, the amount and
concentration of acid is generally not critical. For example, more dilute
acid may be used if the stirring time is extended, but use of the more
concentrated acids is preferred for commercial applications. Suitable
mineral acids include sulfuric acid and polyphosphoric acid, with sulfuric
acid being preferred. It is particularly preferred to use at least 64%
aqueous sulfuric acid in amounts of about 4 to about 15 parts by weight of
acid relative to the total amount of crude organic pigment and pigment
derivative. Although the dissolution rate of the mixture of crude pigment
and pigment derivative in acid can be increased by warming the mixture
(for example, to about 50.degree. C.), it is generally preferable to
dissolve the mixture in acid at or below 35.degree. C. to minimize
sulfonation (when using sulfuric acid) or degradation of the pigment or
pigment derivative. After the acid treatment is completed, the pigment
composition is precipitated by adding the strongly acidic solution to a
liquid in which the pigment and pigment derivative are completely or
almost completely insoluble, preferably water or methanol or other lower
aliphatic alcohols (such as ethanol, propanol, or butanol), as well as
mixtures thereof.
When using sulfuric acid or oleum in the preparation of the
heteroarylamidomethyl or heteroarylthioamidomethyl pigment derivatives or
of the ultimate pigment compositions, the pigment moiety can be
sulfonated. Such sulfonated derivatives can be isolated as the free acid,
an ammonium salt, or a metal salt (including, for example, alkali metal
salts such as those of sodium or potassium, alkaline earth metal salts
such as those of calcium or barium, and Group III metal salts such as
those of aluminum).
In a second preferred method, an organic pigment is blended with a suitable
heteroarylamidomethyl and/or heteroarylthioamidomethyl pigment derivative
using wet or dry blending variants. The dry blending variant comprises (a)
dry blending an organic pigment with about 0.1 to about 20% by weight
(preferably 1 to 10% by weight), based on the organic pigment, of a
pigment derivative of formula (I); and (b) collecting the pigment
composition. The wet blending variant comprises (a) treating an organic
pigment with (1) about 0.1 to about 20% by weight (preferably 1 to 10% by
weight), based on the organic pigment, of a pigment derivative of formula
(I), and (2) about 5 to about 20% by weight (preferably 5 to 15% by
weight), based on the organic pigment, of a liquid in which the organic
pigment is substantially insoluble, thereby forming a suspension of the
treated pigment composition in the liquid; and (b) collecting the pigment
composition. The liquid used for wet blending is a liquid in which the
organic pigment is substantially insoluble, preferably water, a
water-miscible solvent such as methanol or other lower aliphatic alcohols,
or mixtures thereof. It is desirable, but not necessary, for the
heteroarylamidomethyl or heteroarylthioamidomethyl pigment derivative to
be at least partly insoluble in the liquid. Suitable liquids include water
and/or water-miscible organic liquids; including, for example, lower
aliphatic alcohols, such as methanol; ketones and ketoalcohols, such as
acetone, methyl ethyl ketone, and diacetone alcohol; amides, such as
dimethylformamide and dimethylacetamide; ethers, such as tetrahydrofuran
and dioxane; alkylene glycols and triols, such as ethylene glycol and
glycerol; and other such organic liquids known in the art. Other organic
liquids can be used but are generally less preferred. The temperature at
which wet blending is carried out is generally not critical but is usually
maintained between about 5.degree. C. and about 60.degree. C. (preferably
below the boiling point of the liquid).
In a third preferred method, which is particularly useful for preparing
quinacridone pigment compositions, a suitable heteroarylamidomethyl and/or
heteroarylthioamidomethyl pigment derivative is added during or even
before synthesis of the organic pigment being treated such that the
reaction and the treatment processes can take place in situ, at least in
part, as the organic pigment is formed. For example, when preparing
quinacridone pigments, a preferred preparative method comprises (a)
heating, at a temperature of about 80.degree. C. to about 145.degree. C.
(preferably 100.degree. C. to 130.degree. C.), a reaction mixture
comprising (i) 2,5-dianilinoterephthalic acid,
2,5-dianilino-6,13-dihydroterephthalic acid,
2,5-dianilino-3,6-dioxo-1,4-cyclohexadiene-1,4-dicarboxylic acid, or a
derivative thereof having one or more substituents in at least one aniline
ring; a salt or ester of said acid or derivative thereof; or a mixture
thereof, (ii) about 0.1 to about 15 percent by weight (preferably 0. 1 to
10 percent by weight), based on component (a)(i), of a suitable
heteroarylamidomethyl and/or heteroarylthioamidomethyl pigment derivative,
(iii) about 3 to about 20 parts by weight (preferably 3 to 10 parts by
weight), per part of component (a)(i), of a dehydrating agent (preferably
polyphosphoric acid), with the proviso that if either component (a)(i) or
component (a)(ii) is a 2,5-dianilino-6,13-dihydroterephthalic acid or
derivative thereof, reaction step (a) additionally comprises an oxidation
step (which converts the initially formed dihydroquinacridone intermediate
to the corresponding quinacridone); (b) drowning the reaction mixture from
step (a) by adding said reaction mixture to about 3 to about 15 parts by
weight (preferably 5 to 10 parts by weight), per part of component (a)(i),
of a liquid in which the quinacridone pigment is substantially insoluble;
and (c) isolating the quinacridone pigment.
Each of the above methods can be carried out in the presence of one or more
additional pigment derivatives known in the art, particularly sulfonic
acid and sulfonamide derivatives.
Regardless of which of the above methods is used, the resultant pigment
composition is collected by methods known in the art, preferably
filtration followed by a washing step to remove residual acid. Other
collection methods known in the art, such as centrifugation or even simple
decantation, are suitable but generally less preferred. The pigment
composition is then dried for use or for further manipulation before use.
Pigment compositions according to the invention can be obtained by
conditioning organic pigments in the presence of a heteroarylamidomethyl
and/or heteroarylthioamidomethyl pigment derivative, carried out either
instead of or in addition to the preparative methods described above. It
is, of course, possible to include one or more additional pigment
derivatives known in the art, particularly sulfonic acid and sulfonamide
derivatives. Conditioning can be carried out using any of various methods
known in the art, such as solvent treatment or milling in combination with
solvent treatment. Final particle size of the pigment can be controlled by
varying the method of aftertreatment. For example, pigments can be made
more transparent by reducing the particle size or more opaque by
increasing the particle size. Suitable milling methods include dry-milling
methods such as sand-milling, ball-milling, and the like, with or without
additives, or wet-milling methods such as salt-kneading, bead-milling, and
the like in water or organic solvents, with or without additives.
Tinctorial strength and transparency of the pigment can also be affected by
solvent treatment carried out by heating a dispersion of the pigment
composition, often in the presence of additives, in a suitable solvent.
Suitable solvents include organic solvents, such as alcohols, esters,
ketones, and aliphatic and aromatic hydrocarbons and derivatives thereof,
and inorganic solvents, such as water. Suitable additives include
compositions that lessen or avoid flocculation, increase dispersion
stability, and reduce coating viscosity, such as polymeric dispersants (or
surfactants). E.g., U.S. Pat. Nos. 4,455,173, 4,758,665, 4,844,742,
4,895,948, and 4,895,949.
During or after the optional conditioning step it is often desirable to use
various other optional ingredients that provide improved properties.
Examples of such optional ingredients include fatty acids having at least
12 carbon atoms, such as stearic acid or behenic acid, or corresponding
amides, esters, or salts, such as magnesium stearate, zinc stearate,
aluminum stearate, or magnesium behenate; quaternary ammonium compounds,
such as tri›(C.sub.1 -C.sub.4 alkyl)benzyl!ammonium salts; plasticizers,
such as epoxidized soya bean oil; waxes, such as polyethylene wax; resin
acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin;
C.sub.12 -C.sub.18 -paraffin-disulfonic acids; alkylphenols; alcohols,
such as stearyl alcohol; amines, such as laurylamine or stearylamine; and
aliphatic 1,2-diols, such as dodecane-1,2-diol. Such additives can be
incorporated in amounts ranging from about 0.05 to 20% by weight
(preferably 1 to 10% by weight), based on the amount of pigment.
Because of their light stability and migration properties, the pigment
compositions according to the present invention are suitable for many
different pigment applications. For example, pigment compositions
according to the invention can be used as the colorant (or as one of two
or more colorants) for very lightfast pigmented systems. Examples include
pigmented mixtures with other materials, pigment formulations, paints,
printing ink, colored paper, or colored macromolecular materials. The term
"mixtures with other materials" is understood to include, for example,
mixtures with inorganic white pigments, such as titanium dioxide or
cement, or other inorganic pigments. Examples of pigment formulations
include flushed pastes with organic liquids or pastes and dispersions with
water, dispersants, and, where appropriate, preservatives. Examples of
paints in which pigment compositions of the invention can be used include,
for example, physically or oxidatively drying lacquers, stoving enamels,
reactive paints, two-component paints, solvent- or water-based paints,
emulsion paints for weatherproof coatings, and distempers. Printing inks
include those known for use in paper, textile, and tinplate printing.
Suitable macromolecular substances include those of a natural origin, such
as rubber; those obtained by chemical modification, such as acetyl
cellulose, cellulose butyrate, or viscose; or those produced
synthetically, such as polymers, polyaddition products, and
polycondensates. Examples of synthetically produced macromolecular
substances include plastic materials, such as polyvinyl chloride,
polyvinyl acetate, and polyvinyl propionate; polyolefins, such as
polyethylene and polypropylene; high molecular weight polyamides; polymers
and copolymers of acrylates, methacrylates, acrylonitrile, acrylamide,
butadiene, or styrene; polyurethanes; and polycarbonates. The materials
pigmented with the pigment compositions of the present invention can have
any desired shape or form.
The pigment compositions prepared according to this invention are highly
water-resistant, oil-resistant, acid-resistant, lime-resistant,
alkali-resistant, solvent-resistant, fast to over-lacquering, fast to
over-spraying, fast to sublimation, heat-resistant, and resistant to
vulcanizing, yet give a very good tinctorial yield and are readily
dispersible (for example, in plastic materials).
The following examples further illustrate details for the preparation and
use of the compositions of this invention. The invention, which is set
forth in the foregoing disclosure, is not to be limited either in spirit
or scope by these examples. Those skilled in the art will readily
understand that known variations of the conditions and processes of the
following preparative procedures can be used to prepare these
compositions. Unless otherwise noted, all temperatures are degrees Celsius
and all percentages are percentages by weight.
EXAMPLES
Preparation of heteroarylamidomethylquinacridone and
heteroarylthioamidomethylquinacridone derivatives
Nicotinamidomethylquinacridone
##STR7##
To 219 g of 100% sulfuric acid was slowly added with stirring 15.2 g of
(0.10 mol) of N-hydroxymethylnicotinamide at a temperature below
25.degree. C. To the acidic mixture was slowly added 31.2 g (0.10 mol) of
quinacridone. The reaction mixture was then stirred for one hour at a
temperature below 10.degree. C., allowed to warm to room temperature and
stirred for 18 hours. After being held at 60.degree.-65.degree. C. for
three hours, the reaction mixture was cooled to 35.degree. C. and slowly
poured into two liters of iced water. The resultant slurry was stirred for
30 minutes while warming to 15.degree. C. The solid was isolated by
filtration and washed with water. The wet presscake was reslurried with
water and heated to 60.degree. C. for 30 minutes, after which the solid
was isolated by filtration and washed with water. The wet presscake was
dried in an oven at 60.degree. C. to give 31.7 g of
nicotinamidomethylquinacridone.
Di(nicotinamidomethyl)quinacridone
##STR8##
The method described above for the preparation of
nicotinamidomethylquinacridone was repeated except for using 260 g of 100%
sulfuric acid and 30.0 g (0.20 mol) of N-hydroxymethylnicotinamide.
Di(nicotinamidomethyl)quinacridone (24.7 g) was thus obtained.
Thionicotinamidomethylquinacridone
##STR9##
To 210 g of 100% sulfuric acid was added 14.1 g of (0.10 mol) of
thionicotinamide over a period of 15 minutes at a temperature below
15.degree. C. The acidic mixture was stirred for an additional 10 minutes,
after which 3 g (0.10 mol) of paraformaldehyde was added while maintaining
a temperature below 15.degree. C. The reaction mixture was allowed to warm
to room temperature, held at 20.degree.-25.degree. C. for two hours, and
cooled to 10.degree. C. To this mixture was added 31.2 g (0.10 mol) of
quinacridone while the temperature was maintained below 15.degree. C. The
mixture was allowed to warm to room temperature, then held at
60.degree.-65.degree. C. for two hours. After being stirred at room
temperature for 18 hours, the reaction mixture was slowly poured into two
liters of iced water. The resultant slurry was allowed to warm to
20.degree. C. and then stirred for one hour, after which the solid was
isolated by filtration and washed with water. The wet presscake was
reslurried with water and heated for 30 minutes at 60.degree. C., after
which the solid was again isolated by filtration and washed with water.
The wet presscake was dried in an oven at 60.degree. C. to give 34.8 g of
thionicotinamidomethylquinacridone.
2-Furamidomethylquinacridone
##STR10##
To 200 g of 96% sulfuric acid at a temperature below 25.degree. C. was
added 25 g of (0.08 mol) of quinacridone. The acidic mixture was stirred
for 30 minutes, after which 9 g (0.08 mol) of 2-furamide (prepared by the
method described in J. Amer. Chem. Soc., 75, 2370-2372 (1953)) was added
while the temperature was maintained below 35.degree. C. The resultant
mixture was stirred for an additional 30 minutes, after which 2.4 g (0.08
mol) of paraformaldehyde was slowly added. The reaction mixture was heated
at 60.degree.-65.degree. C. for five hours. The mixture was allowed to
cool to room temperature, stirred at room temperature for 18 hours, and
slowly poured into two liters of iced water. The resultant slurry was
stirred for 30 minutes, after which the solid was isolated by filtration
and washed with water. The wet presscake was reslurried with water and
heated for 30 minutes at 60.degree. C., after which the solid was isolated
by filtration and washed with water. The wet presscake was dried in an
oven at 60.degree. C. to give 31.2 g of 2-furamidomethylquinacridone.
2-Thiophenecarboxamidomethylquinacridone
##STR11##
To 210 g of 100% sulfuric acid was added 12 g of (0.09 mol) of
2-thiophenecarboxamide at a temperature below 15.degree. C. The acidic
mixture was stirred for 15 minutes, after which 2.7 g (0.09 mol) of
paraformaldehyde was slowly added. The reaction mixture was stirred for 15
minutes at a temperature below 10.degree. C., allowed to stir at room
temperature for two hours, and again cooled to 10.degree. C. After adding
28.1 g (0.09 mol) of quinacridone, the reaction mixture was held at
60.degree. C. for two hours. The mixture was then allowed to cool to room
temperature, stirred at room temperature for 18 hours, and slowly poured
into two liters of iced water while a temperature below 15.degree. C. was
maintained. The resultant slurry was stirred for one hour, after which the
solid was isolated by filtration and washed with water. The wet presscake
was reslurried with water and heated for 30 minutes at 60.degree. C.,
after which the solid was again isolated by filtration and washed with
water. The wet presscake was dried in an oven at 60.degree. C. to give
39.3 g of 2-thiophenecarboxamidomethylquinacridone.
EXAMPLES 1-12
The preparation and testing of pigment compositions are described in
Examples 1-12.
Differences in hue and chroma for pigments prepared according to the
Examples were measured using an Applied Color System Spectral Sensor (Hunt
Associated Laboratories, Fairfax, Va).
Water-based Paint Tests
Water-based paints tests were carried out using a waterborne base
coat/solvent-borne clear coat system. Aqueous dispersions were prepared
using a mixture of 12.4% AROLON.RTM. 559-G4-70 acrylic resin (Reichhold
Chemicals, Inc.), 3.2% SOLSPERSE.RTM. 27000 hyperdispersant (Zeneca,
Inc.), 1.6% 2-amino-2-methyl-1-propanol (Angus Chemical), and 18% pigment,
which gave a pigment-to-binder ratio of 18:12 and a total solids content
of 30%. The pigment-to-binder ratio was then reduced to 10:40 with
additional AROLON.RTM. 559-G4-70 acrylic resin (total amount 26%) and 25%
CYMEL.RTM. 325 melamine/formaldehyde resin (Cytec Industries), which gave
a total solids content of 50%. Masstone and transparency measurements were
made using films applied at 76 .mu.m and 38 .mu.m wet film thickness,
respectively, and allowed to stand at room temperature for fifteen minutes
and at 100.degree. C. for five minutes. Clear coats containing a mixture
of 80% of AROPLAZ.RTM. 1453-X-50 alkyd resin and 20% CYMEL.RTM. 325
melamine/formaldehyde resin at a total solids level of 57% were then
applied over the base coat at a 76 .mu.m wet film thickness allowed to
stand at room temperature for fifteen minutes and at 121.degree. C. for
fifteen minutes.
Undertone tint paints were prepared from the reduced aqueous dispersions
described above having a pigment-to-binder ratio of 10:40 by adding
additional AROLON.RTM. 559-G4-70 acrylic resin, CYMEL.RTM.325
melamine/formaldehyde resin, and 35% TINT-AYD.RTM. CW-5003 white
dispersion (Daniel Products Company), which gave a pigment-to-binder ratio
of 1:1.1, a total solids content of 55%, and a TiO.sub.2 -to-pigment ratio
of 90:10. Color measurements were made using films applied at 38 .mu.m wet
film thickness and allowed to stand at room temperature for fifteen
minutes and at 100.degree. C. for five minutes. Clear coats were then
applied and baked as described above.
Metallic paints were prepared from the dispersion described above having a
pigment-to-binder ratio of 18:12 using a water-dispersible aluminum
pigment (available as HYDRO PASTE.RTM. 8726 from Silberline Manufacturing
Co., Inc.), AROLON.RTM. 559-G4-70 acrylic resin, and CYMEL.RTM. 325
melamine/formaldehyde resin in quantities that provided a
pigment-to-binder ratio of 1:2, an aluminum-to-pigment ratio of 20:80, and
a total solids content of 43%. Color measurements were made using films
applied at 38 .mu.m wet film thickness and baked as described above. Clear
coats were then applied and baked as described above.
Example 1 (comparison)
Pigmentary 2,9-dimethylquinacridone was prepared in the absence of a
heteroarylamidomethyl or heteroarylthioamidomethyl pigment derivative
according to the invention.
To 300 g of polyphosphoric acid (112% phosphoric acid) heated at 88.degree.
C. was added 68.2 g of 2,5-di(4-methylanilino)terephthalic acid over a
period of 35 minutes, the temperature being maintained below 120.degree.
C. by adjustment of the addition rate. The reaction mixture was heated at
123.degree. C. for two hours. The melt was cooled to 93.degree. C. and
then slowly poured into 494 g of methanol, the temperature being
maintained below 64.degree. C. by external cooling and adjustment of melt
addition rate. The slurry was heated at reflux for one hour, cooled to
below 60.degree. C., diluted with water, collected by filtration, and
washed with water until acid free. The resultant presscake was reslurried
in water. After adjustment of the pH to greater than 7, 5.5 g of 50%
sodium hydroxide was added and the resultant slurry was heated at
90.degree. C. for one hour. The slurry was cooled, filtered, and washed
with water until alkaline free, then reslurried in water. After adjustment
of the pH to 9.5, the slurry was heated at 143.degree. C. for two hours in
a closed system (e.g., a pressure reactor), and cooled to 40.degree. C.
After the slurry was acidified to pH 3.3, an emulsion of 2.2 g of an
anionic surfactant, 30 g of a petroleum distillate, and 80 g of water was
added, and the slurry was stirred for three hours. The wet cake was dried
in an oven at 60.degree. C. to give approximately 60 g of
2,9-dimethylquinacridone as a magenta pigment.
Example 2
2,9-Dimethylquinacridone prepared according to the method of comparison
Example 1 was dry-blended with 10% by weight of
nicotinamidomethylquinacridone. A water-based paint prepared as described
above exhibited reduced viscosity and a bluer tint compared to a paint
prepared using the comparison 2,9-dimethylquinacridone pigment of Example
1.
Example 3 (comparison)
Example 2 was repeated except for using 10% by weight of
phthalidomethylquinacridone. A water-based paint prepared as described
above exhibited a slightly lighter masstone and a slightly decreased
metallic brightness compared to a paint prepared using the pigment of
Example 2 of the invention.
Example 4
2,9-Dimethylquinacridone prepared according to the method of comparison
Example 1 was dry-blended with 10% by weight of
di(nicotinamidomethyl)quinacridone. A water-based paint prepared as
described above exhibited an increased metallic blueness and brightness
compared to a paint prepared using the comparison 2,9-dimethylquinacridone
pigment of Example 1.
Example 5
2,9-Dimethylquinacridone prepared according to the method of comparison
Example 1 was dry-blended with 10% by weight of
thionicotinamidomethylquinacridone. A water-based paint prepared as
described above exhibited reduced viscosity compared to a paint prepared
using the comparison 2,9-dimethylquinacridone pigment of Example 1.
Example 6
Example 5 was repeated except for using 5% by weight of
thionicotinamidomethylquinacridone. A water-based paint prepared as
described above exhibited viscosity and coloristic properties comparable
to a paint prepared using the comparison 2,9-dimethylquinacridone pigment
of Example 1.
Example 7
2,9-Dimethylquinacridone prepared according to the method of comparison
Example 1 was dry-blended with 10% by weight of
2-furamidomethylquinacridone. A water-based paint prepared as described
above exhibited reduced viscosity compared to a paint prepared using the
comparison 2,9-dimethylquinacridone pigment of Example 1.
Example 8
Example 7 was repeated except for using 5% by weight of
2-furamidomethylquinacridone. A water-based paint prepared as described
above exhibited reduced viscosity compared to a paint prepared using the
comparison 2,9-dimethylquinacridone pigment of Example 1.
Example 9
Pigmentary 2,9-dimethylquinacridone was prepared exactly as described in
comparison Example 1 except that 3.4 g of 2-furamidomethylquinacridone (5%
by weight relative to the 2,5-di(4-methylanilino)-terephthalic acid) was
included in the ring-closure reaction. A water-based paint prepared as
described above exhibited a deeper, brighter, more transparent masstone
and increased metallic blueness and brightness compared to a paint
prepared using the comparison 2,9-dimethylquinacridone pigment of Example
1.
Example 10 (comparison)
Example 9 was repeated except for using 10% by weight of
phthalidomethylquinacridone. A water-based paint prepared as described
above exhibited a lighter masstone and a dramatically decreased tint and
metallic brightness compared to a paint prepared using the pigment of
Example 9 of the invention.
Example 11
2,9-Dimethylquinacridone prepared according to the method of comparison
Example 1 was dry-blended with 10% by weight of
2-thiophenecarboxamidomethylquinacridone. A water-based paint prepared as
described above exhibited reduced viscosity compared to a paint prepared
using the comparison 2,9-dimethylquinacridone pigment of Example 1.
Example 12
Example 11 was repeated except for using 5% by weight of
2-thiophenecarboxamidomethylquinacridone. A water-based paint prepared as
described above exhibited reduced viscosity compared to a paint prepared
using the comparison 2,9-dimethylquinacridone pigment of Example 1.
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